Polymerization of vinylidene compounds using organic peroxide, organic sulfur and quaternary ammonium compounds as catalysts



United States Patent O POLYMERIZATION OF VlNYLIDENE COM- POUNDS USING ORGANIC PEROXIDE, ORGANIC SULFUR AND QUATERNARY LAIVIMYS I SNIUM COMPOUNDS AS CATA Erich Biider, Hanan am Main, Otto Schweitzer, Konigstein, Taunus, and Wilhelm Querfurth, Oberursel, Taunus, Germany, assignors to Deutsche Goldund Silber-Scheideanstalt vormals Roessler, Frankfurt am 5 Main, Germany No Drawing. Filed July 25, 1955, Ser. No. 524,272- Claims priority, application Germany July 30, 1954 5 Claims. ,(Cl. 260-775) This invention relates to a process for the polymerisation of organic compounds. a

It is known to polymerise organic compounds having terminal or intermediate carbon to carbon double bonds. These compounds include, for example, styrene and its derivatives, acrylic and methacrylic acids and esters thereof, vinyl compounds, acrylonitrile, butadiene, chlorbutadiene and dimethylbutadiene, alone or in admixture with one another. solution or emulsion or in bulk. For many purposes it is advantageous to polymerise a system which consists of a solution or suspension of a high-moleculanweight substance in a polymerisable monomeric substance.

Such mixtures can, for example, be employed with good results for dental purposes.

Redox systems have been proposed as catalysts for the polymerisation of these substances, which systems contain on the one hand oxygen, such for example as atmospheric oxygen, but preferably oxygen in peroxide form, such for example as benzoyl peroxide. Sulphinic acids or salts thereof, alpha-hydroxysulphones or salts thereof, sulphoxyl compounds, such as sodium formaldehyde sulphoxylate obtained by reacting sodium hydrosulphite with formaldehyde or the corresponding zinc, calcium or bismuth salts, alpha-amino-sulphones, especially of secondary or tertiary amines, and mercaptans, have been proposed-as the reducing components of such Redox systems.

It has now been found that the polymerisation of such 2,946,770 Ce Patented July 26, 1960 5 "phonium, arsonium or stibonium compounds or the cor- "responding compounds of mercury, zinc, bismuth, tin or lead.

Organic ammonium, sulphonium or oxonium compounds of the general formulae:

adding to them small quantities of heavy metal com- These compounds can be' polymerised 11 1 5; Such or' mp a wpp or iron p d and/or small quantities of monohydric or polyhydric aliphatic'alcohols, such for exampleas methanol, ethato the mixture organic or inorganic acids, such as acrylicacid, methacrylic acid or phosphoric acid, in such quantities that any free bases present are neutralised.

35, Finally, it has proved advantageous in many cases not to keep the polymerisation mixture'wholly water-free but to arrange for the presence of small quantities of water.

Table I below summarises the results of experiments with mixtures in accordance with the invention. In each 40 experiment a mixture of 1.3 g. of polymeric methyl 'methacrylate with 0.75 ml. of monomeric methyl methacrylate was polymerised with the addition of the substances mentioned in the table at an initial temperature of 22 to 23 C. and the time required to reach the maxi- 45 mum temperature was recorded. f 1

' The results of a further series of experiments are se out in'Iable II. W

Of the above compounds the salts of quaternary ammethyl chloride.

TABLE I Polymcrisa- Quaternary compounds S-containing initiator Peroxide Further additions iignmturgg,

1. 0.5% Triethyl-benzyl-am- 2% Toluene-Sulphinic acid 2% McthanoL. 10v Ou (as 8.

monium chloride. glczcltyelacet- 2. 0.5% Octadecyl-di-methyl- 2% Na-toluene-sulphinate .do 10- Cu 5% Meth- 1 1.

benzyl-amoniuru chloride. acryhc 801d., 3. 0.5% octadecyl-dlil-metihyl- -do do 10 Ou 0.5%H P04--- 11.5.

benzyl-amoniumc lori e. i 4. 0.5% Dodeeyl-dibenzyldo 1%benz oyl d0 10 Ou++ 3% Meth- 11.5.

methyl-ammonium chloride 1 peroxide. acrylic acld. 5. 0.5% Phenylethyl-dibutyl- 1% Oa-benzene-sulphinate 1.5% ben- 57 Fe- (as 7% Methethyl-ammonium chloride. 7 zoyl pernaphthem. acrylic acid 9.75.

oxide. ate 0.6%H P04 6. 0.5% Dodecyl-debenzyl- 2% onsornrsorornon 2% Methanol 107 Ou++ 7. methyl amonium chloride. 7 7. 0.5% Triethyl-benzyl-am- 2% (CHaCaH4SOzCH2)2NCgHr l0 'yCu 13.5.

monium chloride. 8. 0.5% Ethanol-diethyl-ben- 2% (GHaOdHrsozCHmNCgH -4--. 2% Methanol 10 Cur 9.

zyl-ammoniumchloride. V 9. 0.5% Octadecyl-di-methyl- 2% (onaoamsozonomosm I 2% 1.3-Butane- 10 Gu 9.

Zbenzyl-ammonimn chloride. g Y dlol. 10. 0.5% Octadecy1-di-methyl- 2% (OH3O6H4SozOHmNozHrOsH 2% Methanol. 10 Cu 10.

benzyl-ammonium chloride. 7 I 7 v 11; 0.5% Dodecyl dibenzyl- 1% (CH3CaH4SO2CH2)2NH 1%benz oyl do 10 CW" 10.

methyl-ammonium chloride. peroxlde. 12.05% Dodecyl Ldibenzyl- 1% Dodecylmercaptan d0 10y Ou++ 5% acrylic acid. 11,

"2. The process of claim 1 in which said polymerization is carried out in the presence of a catalytic amount of a heavy metal polymerization accelerating compound selected from the group consisting of copper and iron salts.

3. The process of claim 1 in which said polymerization is carried out in the presence of a catalytic amount of an aliphatic alcohol.

' 4. The process of claim 1 in which said polymerization is carried out in the presence of a suflicient amount of an acid compound to neutralize any free base present.

5. The process of claim 1 in which said polymerization is carried out in the presence of a small quantity of water.

References (Iited in the file of this patent UNITED STATES PATENTS Castan et a1 Sept. 11, 1951 Uraneck et a1. Dec. 21, 1954 Blanchette et al Aug. 9, 1955 Barney May 1, 1956 Bredereck et a1. June 12, 1956 Bredereck et al Aug. 7, 1956 Bredereck et a1. Jan. 29, 1957 OTHER REFERENCES Fueno et al.: Journal of Polymer Science XV, pages 594-595 (1955). 

1. A PROCESS FOR THE MASS POLYMERISATION OF A CH2=C< COMPOUND ORGANIC COMPOUND CONTAINING POLYMERISING A POLYMERIZABLE ORGANIC COMPOUND CONTAINING TERMINAL >C=CH2 GROUP IN THE PRESENCE OF CATALYTIC AMOUNT OF AN ORGANIC PEROXIDE, AN ORGANIC SULPHUR COMPOUND SELECTED FROM THE GROUP CONSISTING OF SULPHINIC ACIDS AND SALTS THEREOF, ALPHA-HYDROSULPHONES, SULPHOXYLATES, ALPHAAMINO-SULPHONES AND MERCAPTANS, AND AN ORGANIC QUATERNARY AMMONIUM COMPOUND THE ORGANIC GROUPS OF WHICH ARE SELECTED FROM THE GROUP CONSISTING OF ALKYL AND ARALKYL RADICALS. 